Formulations and methods

ABSTRACT

Formulations for fracturing fluids are prepared by mixing a granulated water-soluble friction reducing polymer with an invert polymer emulsion friction reducing formulation optionally in the presence of an organophilic clay, without the need for specialized field equipment. The mixture can be dosed into water to produce a fracturing fluid which is found to be technically highly advantageous and cost-effective.

TECHNICAL FIELD

This invention relates to formulations and methods and particularly,although not exclusively, relates to formulations for use as frictionreducers in fracturing fluids for high rate hydraulic fracturing ofsubterranean formations.

BACKGROUND

Hydraulic fracturing is a process used to produce oil and gas fromunconventional reservoirs such as coal beds, tight sandstones andshales. In the process, a fracturing fluid is injected at a rate andpressure necessary to cause formation failure by inducing fractures orcracks in the formation. These cracks originate at the well-bore andradiate out into the formation. A common practice in unconventionalreservoirs is to initiate entry into the reservoir with a small slug ofacid, pumped at low rates, followed by low viscosity aqueous fluid(mainly comprising water) pumped at an increasing rate, until a designedhigh rate is achieved. High rates can typically range from 50 to 100barrels per minute.

Once a treatment rate is achieved, low concentrations of propping agentor proppant are added to the fluid. Typically, most proppant comprisessmall-sized sand, such as 0.25 pounds of 100 mesh sand per gallon ofwater. As the fracturing process proceeds, the amount of sand issystematically increased and, at some point, the size of the sand may beincreased to 40/70 or 30/50 mesh. The resulting sand pack formed in thefracture is orders of magnitude more permeable than the formation strataand, accordingly, the pack is able to maintain a conductive pathway fromthe reservoir to the well-bore for the recovery of the reservoir fluids.Proppant concentrations will normally range from 200,000 lb to 500,000lb per fracturing stage and the water can range from 2,000 to 11,000barrels of water. The number of fracturing stages on a horizontal wellcan range from 5 to 75 stages, but more commonly 10 to 50 stages, andmost commonly, 15 to 40 stages.

Most treatment fluids used in newly drilled horizontal wells, are pumpedthrough well-bore casings having 4.5 inch to 5.5 inch diameters. As aconsequence of the pump rates normally used, the diameter of the casingand the viscosity and density of the fluid, the fracturing fluidexhibits a flow regime that is in turbulent rather than laminar flow.This high degree of turbulence increases the pumping pressure, commonlyto levels that can exceed the casing burst pressure, which ispotentially devastating to the well integrity. To address this problemand prevent the treatment fluid from reaching dangerously highpressures, small amounts (e.g. 25 to 700 ppm) of friction reducerpolymer are commonly added to the fracturing fluid.

Friction reducers are typically polyacrylamide polymers or co-polymersthat can be either anionically or cationically charged. A commonly usedpolyacrylamide co-polymer is composed of a random distribution ofacrylamide and a salt of an acrylate monomer. The acrylate monomer canbe a sodium, ammonium or potassium acrylate salt. When such a co-polymeris added to a fracturing fluid, the salt ionizes to leave negativecharges on the polymer. These negative charges, causing charge repulsionbetween the acrylate groups, can increase the hydrodynamic volume of thepolymer, causing an enhancement of the friction reductioncharacteristics. The acrylate salts contribution to the polymer canrange from 0 to 50% (by molar ratio), for example between 5 and 40% andmost commonly between 10 and 30%.

In addition to acrylate salts, sulfonate salts can be used for the samepurpose, with the added benefit of being more tolerant to saline water.Water used in fracturing fluids may vary from relatively fresh tomoderately saline. Sulfonate salts used in a polyacrylamide co-polymerare much more tolerant to salts, enabling a sulphonate based co-polymerto be used in waters containing greater than 50000 ppm chloride.

A polyacrylamide co-polymer for a fracturing fluid is commonlymanufactured as an invert polymer emulsion, this having micron andsub-micron sized polymer particles dispersed in an oil carrier andstabilized with one or more non-ionic surfactants. The polymer contentin the emulsion can range from 5 to 50 wt % but commonly is between 10and 40 wt % and, most commonly, is between 15 and 30 wt %. One advantageof the invert emulsion is its operational simplicity of use duringpumping operations. Typical loadings in a fracturing fluid range from to1,000 ppm, but more commonly are 50 to 500 ppm and most commonly arebetween 75 and 300 ppm. The most common concentration equates to a fieldconcentration of 0.25 to 1.0 gallons of friction reducing emulsion per1,000 gallons of fracturing fluid (referred to as “gallons per thousand”or “gpt”). The low field concentrations of 0.25 to 1.0 gpt of frictionreducers added to fracturing field equipment such as a blender, and inparticular, a blender tub, makes the use of the invert emulsions easy tomanage.

Although easy to handle and pump, an invert emulsion is relativelyexpensive due, in part, to the cost of oil and surfactants used to makethe emulsion. The amount of water treated with friction reducers canrange from 4 to 15 million gallons and the amount of friction reducerscan range from 1,000 gal to 15,000 gallons of invert emulsion per well.Consequently, the cost of the friction reducers can be a majorcontribution to the cost of the fracturing treatment.

Granulated polyacrylamide polymers and co-polymers are availablecommercially at a lower cost than invert emulsions. However, althoughthe cost of the granulated friction reducers is substantially less, easeof use in fracturing treatments is more operationally complicated. Forexample, making a concentrated aqueous solution of the frictionreducers, as in U.S. Pat. No. 8,211,835, to be diluted by pumping smallvolumes of the aqueous solution into the fracturing fluid is notpractical. The friction reducers are high molecular weight water solublepolymers. When added to water and hydrated, except in very diluteconcentrations, the polymers can significantly increase the viscosity ofthe solution. Most acrylamide polymers or co-polymers are limited inconcentration up to about 3 wt % before the solution becomes too viscousto be pumped in a fracturing application. In addition, the costs oftransportation, storage and handling of formulations which are mainlywater, with up to 3 wt % polymer, makes the associated costsunattractive. Another disadvantage of granulates is they need to bebatch or pseudo-batch processed to allow adequate time for the hydrationof the concentrate—this normally takes 15 to 60 min. Because of thishydration time, addition of the granules in a continuous additionprocess, commonly used in fracturing treatments, is ineffective andimpractical.

Another approach is to provide equipment in the vicinity of a well thatcan assist the metering and hydration of granulated polyacrylamidepolymers or co-polymers. However, in addition to making an aqueousconcentrated solution that can be difficult to pump, implementing andmanaging the process will be expensive, particularly when consideringthe cost of the equipment, fuel needed to operate the equipment,maintenance and additional personnel required. Overall operating costcan be similar to the operating cost of the invert polymer emulsionprocess.

It follows that there is a need for a friction reducer which is lessexpensive in use than polyacrylamide-based invert emulsions whilstavoiding the problems of use of granulated polyacrylamide polymers orco-polymers. Furthermore, it is, of course, desirable for any newfriction reducer to have performance which matches or surpasses existingreducers. In particular, it is desirable for a friction reducer toreduce friction in use as much as possible and for maximum frictionreduction to be achieved rapidly, with minimum delay between mixing ofthe friction reducer with water of a fracturing fluid and attainment ofthe maximum friction reduction in the fracturing fluid. If greaterfriction reduction can be achieved, the speed and/or pressures generatedin pumps used to inject the fracturing fluid into a formation can bereduced; or, alternatively, the speed and/or pressures generated may bemaintained at a high level, with the greater friction reduction achievedleading to delivery of fracture fluid at a higher pressure at a fractureface, thereby improving fracturing performance. As a result, it may bepossible to reduce the number of fracture stages required in fracturinga subterranean formation.

It is an object of preferred embodiments of the present invention toaddress the above described problems.

It is an object of preferred embodiments to provide a formulation foruse in friction reduction which is less expensive than a comparablepolyacrylamide invert emulsion and/or is advantageous over use ofgranulated polyacrylamides.

It is an object of preferred embodiments to provide a formulation whichrelatively rapidly inverts in use so its friction reducing effect is notsignificantly delayed in use after contact with water used in thefracturing process.

It is an object of preferred embodiments to provide a formulation whichproduces a high level of friction reduction.

According to a first aspect of the invention, there is provided aformulation (A), for example for use in a fracturing fluid, theformulation (A) comprising:

-   -   (i) a fluid (D) comprising an oil phase; and    -   (ii) particles of a water-soluble polymer (C).

Unless otherwise stated herein, a reference to “ppm” refers to“parts-per-million by weight”; and “wt %” refers to the % of a componenton a weight-for-weight basis.

Said particles of said polymer (C) are preferably dispersed in said oilphase, suitably as solid discrete particles.

The fluid (D) may be any fluid which includes a chemical additive foruse in a fracturing fluid. For example, said fluid (D) may include anyadditive which it is desired to include in a fracturing fluid, forexample selected from friction reducers (e.g. water soluble polymers),corrosion inhibitors, proppant particulates, acids, fluid loss controladditives, biocides, surfactants and scale inhibitors, clay controladditives, foamers, paraffin inhibitors, gelling agents, pH adjustmentadditives, buffers, cross-linkers, oxidizing agents, enzymes and geldegrading agents. Said fluid (D) preferably includes a friction reducer,for example a water-soluble polymer.

Said fluid (D) is preferably an inverse emulsion comprisingwater-soluble polymer (B) and said oil phase. Said polymer (B)preferably includes acrylamide repeat units.

As hereinafter described, formulation (A) may be technicallyadvantageous relative to comparable formulations since it invertsrapidly on contact with water of a fracturing fluid (so the time todeliver target friction reduction may be relatively low); and itproduces higher friction reduction. Additionally, formulation (A) may becheaper to manufacture and purchase compared, for example to aformulation consisting of an inverse emulsion alone which includes acomparable level of friction reducing additive, for example a polymercomprising acrylamide repeat units. However, since the equipment used tomanipulate and deliver formulation (A) to produce a fracturing fluid isthe same as used for a formulation consisting of an inverse emulsion,there are no additional costs involved in using the formulation (A). Inaddition, the formulation (A), because of its rapid polymer hydration,can be used in a continuous addition process. Advantages of preferredformulations are described in the specific examples which follow.

Preferably, the formulation (A) is for addition to an aqueous liquid,for example water, to produce a fracturing fluid which can be used infracturing a subterranean formation. The formulation (A) is suitablyused to reduce the coefficient of friction of the aqueous liquid duringturbulent flow, for example during hydraulic fracturing of asubterranean formation. As a consequence, a pump used to inject afracturing fluid may be operated at a reduced speed and/or pressure; orfor a given pump pressure, more pressure from the pump may be conveyedto the fracture face. The formulation (A) is suitably used to lower thefriction or drag by suppressing the turbulence present in high velocitygradient water of said fracturing fluid and, consequently, the water canbe pumped at higher rates. The formulation (A) may also reach itsmaximum level of friction reduction very rapidly.

Said fluid (D), for example said inverse emulsion, may comprise at least15 wt %, preferably at least 25 wt %, of said oil phase. The formulation(A) may include less than 70 wt % or less than 50 wt % of said oilphase. Polymer (B) is suitably dispersed in the oil phase.

Said fluid (D), for example said inverse emulsion may comprise at least15 wt %, preferably at least 25 wt % of polymer (B). It may include lessthan 50 wt % or less than 40 wt % of polymer (B). The aforementionedamount of polymer (B) is suitably on a dry matter basis.

Polymer (B) is suitably hydrated. For example polymer (B) mayincorporate up to 70 wt %, 60 wt %, 50 wt % or 40 wt % water. Polymer(B) suitably includes at least 10 wt %, at least 14 wt % or at least 20wt % water. In said fluid (D), for example said inverse emulsion,polymer (B) is suitably a hydrated polymer which is dispersed within theoil phase. The hydrated polymer is suitably in the form of micron orsub-micron particles (e.g. 0.1-100 μm, preferably 0.5 to 10 μm). Theinverse emulsion suitably includes a surface active agent to stabilisethe emulsion.

Said fluid (D), for example said inverse emulsion may comprise at least15 wt % water, preferably at least 20 wt % water. It may include lessthan 40 wt % water. The water may hydrate polymer (B).

In a preferred embodiment, said fluid (D), for example said inverseemulsion includes 15-40 wt % of said oil phase, 15-40 wt % of polymer(B) and 15-40 wt % of water. Said fluid (D) may include 1-10 wt % ofsurface active agent(s) as herein described.

Preferably, said polymer (B) is an ionic polyacrylamide. Polymer (B) mayinclude 0-50 mol %, preferably 5-40 mol %, more preferably 10-30 mol %of ionic repeat units.

The balance suitably comprises non-ionic acrylamide repeat units. Whilstpolymer (B) may be an anionic or cationic polyacrylamide, it ispreferably an anionic polyacrylamide. Polymer (B) may be partiallyhydrolysed acrylamide.

Said polymer (B) preferably includes a repeat unit which includes anoptionally substituted acrylamide, for example an alkylacrylamide (e.g.methacrylamide) or N,N-dialkylacrylamide (e.g. N,N-dimethylacrylamide).Said optionally-substituted acrylamide may be of formula I

wherein R⁵, R⁶ and R⁷ independently represent a hydrogen atom or anoptionally-substituted (preferably unsubstituted) C₁₋₄ alkyl, preferablyC₁₋₂ alkyl, more preferably a methyl group.

In formula I, R⁵, R⁶ and R⁷ preferably represent hydrogen atoms.

On average, the ratio of the number of other repeat units in polymer (B)divided by the number of repeat units of formula I may be less than 0.6,0.5, 0.4, 0.3 or 0.2. Said ratio may be at least 0.0025, at least 0.005,at least 0.05 or at least 0.1.

Said polymer (B) may include (e.g. in combination with repeat unit offormula I) a repeat unit which includes an acrylate or sulfonate moiety,for example an acrylate or sulfonate salt, or a pyrrolidone moiety.Polymers which include sulfonate salts may be preferred when theformulation is used with water which includes high levels of hardnessions, for example magnesium, calcium, strontium, barium or ferrous ions.

Said polymer (B) may include a repeat unit of formula I in combinationwith:

-   -   a repeat unit comprising a moiety of formula II

wherein the O* moiety is an O⁻ moiety or is covalently bonded to anotheratom or group;

-   -   a repeat unit comprising a vinyl pyrrolidone moiety; or a repeat        unit comprising a moiety of formula III

wherein R¹ and R² are independently selected from a hydrogen atom and anoptionally-substituted alkyl group. An optionally-substituted alkylgroup may define an electrically neutral hydrophobe. Anoptionally-substituted alkyl group may incorporate an —SO₃R³ moietywherein R³ is selected from a hydrogen atom and a cationic moiety, forexample an alkali metal cation, especially Na⁺. Saidoptionally-substituted alkyl group may include 1 to 36, preferably 1 to20, more preferably 1 to 10 carbon atoms. Said repeat unit may bederived from and/or based on AMPS.

Polymer (B) may be derived from one or more of the following monomers:

Cationic monomers—Methacryloyloxyethyltrimethylammonium chloride,Methacrylamidopropyltrimethylammonium chloride,Acryloyloxyethyltrimethylammonium chloride, Dimethyldiallylammoniumchloride;

Anionic monomers—Sodium Acrylate, Sodium 2-Acrylamido-2-methylpropanesulfonate;

Non-ionic Monomers—Acrylamide, Methacrylamide, N,N Dimethylacrylamide,Vinyl pyrolidonone.

Polymer (B) may include monovalent (e.g. NH₄ ⁺. Li⁺, Na⁺, K⁺, Rb⁺ orCs⁺), divalent (e.g. Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Fe²⁺, Cu²⁺ or Zn²⁺)or trivalent (e.g. Fe³⁺ or Al³⁺) cations. It preferably includesmonovalent cations, with Na⁺ being preferred.

Said polymer (B) preferably includes acrylamide repeat units andacrylate, for example sodium acrylate, repeat units.

Said polymer (B) may have a molecular weight of at least 200,000Daltons, suitably at least 500,000 Daltons, preferably at least1,000,000 Daltons. The molecular weight may be less than 50,000,000Daltons or less than 30,000,000 Daltons. Molecular weight, describedherein, may be measured by Measurement of Intrinsic Viscosity (see ISO1628/1-1984-11-01); and using Intrinsic Viscosity/Molecular WeightCorrelation via the Mark-Houwink Equation.

Fluid (D) may be selected from a wide range of emulsion typepolyacrylamides including, for example, KemFlow A-4251, KemFlow A4355,KemFlow A-4356, KemFlow A-4358, KemFlow A-4361. KemFlow A-4366 (Kemira,Atlanta, Ga., USA); FLOJET DR-7000FLOJET DR-3046 (SNF, Riceboro, Ga.,USA); Sedifloc 320A, and Sedifloc, 331A (3F Chimica, Charlotte, N.C.,USA) containing anionic; and Alcomer-788 and Alcomer-889 (BASF, FlorhamPark, N.J., USA) as cationic polyacrylamide emulsions.

Said oil phase of formulation (A) suitably comprises a hydrophobicliquid which is suitably inert. Said hydrophobic liquid may be ahydrocarbon. It may be selected from paraffinic hydrocarbons, napthenichydrocarbons, aromatic hydrocarbons, benzene, xylene, toluene, mineraloils, diesel oil, kerosenes, naphthas (including hydrotreated naphtha),petrolatums, branch-chain isoparaffinic solvents, branch-chainhydrocarbons, saturated, linear, and/or branched paraffin hydrocarbonsand combinations thereof. Said liquid may include a natural, modified orsynthetic oil; or a vegetable oil such as canola oil, coconut oil,rapeseed oil and the like.

When said fluid (D), for example said inverse emulsion, is stabilised bya surface active agent, said surface active agent may have an HLB(hydrophilic-lipophilic balance) value between 2 and 10, in some casesbetween 3 and 9 and in other cases between 3 and 7.

As used herein, HLB is calculated using the art known method ofcalculating a value based on the chemical groups of the molecule. Themethod uses the following equation:

HLB=7+m*Hh+n*HL

where m represents the number of hydrophilic groups in the molecule, Hhrepresents the value of the hydrophilic groups, n represents the numberof lipophilic groups in the molecule and HL represents the value of thelipophilic groups.

Non-limiting examples of suitable surface active agents include:

-   -   fatty acid esters of mono-, di- and polyglycerols, for instance        the monoleate, the dioleate, the monostearate, the distearate        and the palmitostearate. These esters can be prepared, for        example, by esterifying mono-, di- and polyglycerols, or        mixtures of polyhydroxylated alcohols such as ethylene glycol,        diethylene glycol, dipropylene glycol, 1,4-butanediol,        1,2,4-butanetriol, glycerol, trimethylolpropane, sorbitol,        neopentyl glycol and pentaerythritol;    -   fatty acid esters of sorbitan, for instance sorbitan monoleate,        sorbitan dioleate, sorbitan trioleate, sorbitan monostearate and        sorbitan tristearate;    -   fatty acid esters of mannitol, for instance mannitol monolaurate        or mannitol monopalmitate;    -   fatty acid esters of pentaerythritol, for instance        pentaerythritol monomyristate, pentaerythritol monopalmitate and        pentaerythritol dipalmitate;    -   fatty acid esters of polyethylene glycol sorbitan, more        particularly the monooleates;    -   fatty acid esters of polyethylene glycol mannitol, more        particularly the monooleates and trioleates;    -   fatty acid esters of glucose, for instance glucose monooleate        and glucose monostearate;    -   trimethylolpropane distearate;    -   the products of reaction of isopropylamide with oleic acid;    -   fatty acid esters of glycerol sorbitan;    -   ethoxylated alkylaines;    -   sodium hexadecyl phthalate;    -   sodium decyl phthalate; and    -   oil-soluble alkanolamides.

Suitable active agents include those sold under the trade marks SPAN™and TWEEN™.

The total amount of surface active agents in said fluid (D), for examplesaid inverse emulsion, may be at least about 0.1 wt %, at least 0.5 wt%, or at least 1 wt %. The total may be 10 wt % or less than 5 wt % orless than 2.5 wt %.

Water soluble polymer (C) is preferably substantially insoluble in theoil phase of said fluid (D), for example said inverse emulsion. It ispreferably soluble in water, for example at a concentration of at least10, 20 or 30 wt %.

Said water soluble polymer (C) preferably includes oxygen atoms; it ispreferably capable of hydrogen bonding with water.

Said water soluble polymer (C) may include one or more moieties,suitably in a repeat unit, selected from —C(O)NH₂, —COO⁻, —O— andquaternary ammonium, for example alkyl quaternary ammonium, such as in—N⁺(CH₃)₃ moieties. Moiety —C(O)NH₂ may be part of an acrylamide repeatunit. Moiety —COO⁻ may be part of an acrylate (e.g. a salt of an acrylicacid) repeat unit. Moiety —O— may be part of an ether or a hydroxylmoiety.

In one embodiment, said polymer (C) is poly(ethylene oxide). It may havea weight average molecular weight between 100,000 and 20,000,000Daltons, for example from 1,000,000 to 10,000,000 Daltons.

In a preferred embodiment, said polymer (C) includes an acrylamiderepeat unit. It is preferably a polyacrylamide and, more preferably, isa partially hydrolysed polyacrylamide. Preferably, polymer (C) is anionic polyacrylamide. Polymer (C) may include 0-50 mol %, preferably5-40 mol %, more preferably 10-30 mol % of ionic repeat units. Thebalance suitably comprises non-ionic acrylamide repeat units. Whilstpolymer (C) may be an anionic or cationic polyacrylamide, it ispreferably an anionic polyacrylamide.

Said polymer (C) preferably includes a repeat unit which includes anacrylamide, for example of formula I described above.

On average, the ratio of the number of other repeat units in polymer (C)divided by the number of repeat units of formula I may be less than 0.6,0.5, 0.4, 0.3 or 0.2. Said ratio may be at least 0.0025, at least 0.005,at least 0.05 or at least 0.1.

Said polymer (C) may include a repeat unit which includes an acrylate,sulfonate or pyrrolidone moiety, for example an acrylate or sulfonatesalt. Polymers which include sulfonate salts may be preferred when theformulation is used with water which includes high levels of hardnessions, as described above.

Said polymer (C) may include a repeat unit of formula I as describedabove in combination with:

-   -   a repeat unit comprising a moiety of formula II as described        above; or    -   a repeat unit comprising a vinylpyrrolidone moiety; or    -   a repeat unit comprising a moiety of formula III as described        above;

wherein R¹ and R² are independently selected from a hydrogen atom and anoptionally-substituted alkyl group. An optionally-substituted alkylgroup may define an electrically neutral hydrophobe. Anoptionally-substituted alkyl group may incorporate an —SO₃R³ moietywherein R³ is selected from a hydrogen atom and a cationic moiety, forexample an alkali metal cation, especially Na⁺. Saidoptionally-substituted alkyl group may include 1 to 36, preferably 1 to20, more preferably 1 to 10 carbon atoms.

Polymer (C) may be derived from one or more of the following:

Cationic monomers—Methacryloyloxyethyltrimethylammonium chloride,Methacrylamidopropyltrimethylammonium chloride,Acryloyloxyethyltrimethylammonium chloride, Dimethyldiallylammoniumchloride;

Anionic monomers—Sodium Acrylate, Sodium 2-Acrylamido-2-methylpropanesulfonate;

Non-ionic Monomers—Acrylamide, Methacrylamide, N,N Dimethylacrylamide,Vinyl pyrolidonone.

Polymer (C) may include monovalent (e.g. NfV. Li⁺, Na⁺, K⁺, Rb⁺ or Cs⁺),divalent (e.g. Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Fe²⁺, Cu²⁺ or Zn²⁺) ortrivalent (e.g. Fe³⁺ or Al³⁺) cations. It preferably includes monovalentcations with Na⁺ being preferred.

Said polymer (C) preferably includes acrylamide repeat units andacrylate, for example sodium acrylate, repeat units.

Said polymer (C) may have a molecular weight of at least 200,000Daltons, suitably at least 500,000 Daltons, preferably at least1,000,000 Daltons. The molecular weight may be less than 50,000,000Daltons or less than 30,000,000 Daltons. Molecular weight may bemeasured as described above.

Examples of polymer (C) include solid (powderous) polyacrylamidesincluding KemFlow A-5156, KemFlow A-5157, KemFlow A-5251, KemFlowA-5252. KemFlow A-5253, KemFlow A-5254, KemFlow A-5351, KemFlow A-5352,KemFlow A-5353, KemFlow A-5354, KemFlow A-5356 (Kemira, Atlanta, Ga.,USA); Sedifloc 7030HM, Sedifloc 7030HHM (3F Chimica, Charlotte, N.C.,USA).

As described above, said particles of said polymer (C) are preferablydispersed in said oil phase, suitably as solid discrete particles. Theparticles may be in the form of powder, granules or flake. Unlessotherwise stated, particles sizes are measured as hereinafter described.Said particles preferably have a mean particle diameter of at least 100μm, at least 200 μm or at least 300 μm. Said mean particle diameter maybe less than 1000 μm, for example less than 700 μm or less than 500 μm.

At least 90 wt %, preferably at least 98 wt %, more preferably about 100wt % of said particles of said water soluble polymer (C) have a diametergreater than 1 μm, greater than 10 μm or greater than 20 μm. Saidparticles of said water soluble polymer (C) suitably have a diameterless than 2000 μm, or less than 1100 μm.

Said particles preferably include at least 85 wt %, preferably at least95 wt % of said polymer (C). Said particles may include less than 15 wt%, preferably less than 5 wt % water.

In formulation (A), a ratio (X) defined as the parts by weight(hereinafter pbw) of said fluid (D) (e.g. said inverse emulsion) dividedby the pbw of said particles is suitably in the range 1 to 12,preferably in the range 2 to 10, more preferably in the range 3 to 8.

In formulation (A), a ratio (Y) defined as the pbw of polymer (B)divided by the pbw of polymer (C) is suitably in the range 5:1 to 1:5,preferably 3:1 to 1:3, more preferably in the range 2:1 to 1:2.

In formulation (A), a ratio (Z) defined as the pbw of said oil phasedivided by the pbw of polymer (C) is suitably in the range of 0.1 to 2,preferably in the range 0.1 to 1.2, more preferably in the range 0.3 to1.0.

Said formulation (A) may include a suspending agent to facilitatesuspension of said granules in the formulation. Said formulation mayinclude less than 1 wt %, for example less than 0.75 wt % of suspendingagent. It may include at least 0.1 wt % of suspending agent.

Said suspending agent may be organophilic. It is suitably insoluble informulation (A). It is preferably a clay, for example an organophilicclay.

The organophilic clay, which associates with oily surfaces and rejectsaqueous surfaces, may be the reaction product of purified smectite clay(such as hectorite, bentonite, attapulgite, sepiolite, montmorillonate,etc.) and a quaternary ammonium salt. It includes coated clay (orlignite) such as clay coated with a fatty-acid quaternary amine. Thecoating imparts dispersability of the clay in the oil. Exemplaryorganophilic clays include those disclosed in U.S. Patent PublicationNo. 20070197711 and U.S. Patent Publication No. 20100305008, hereinincorporated by reference. Included here are organo bentonites such asBENTONE® clays of Elementis Specialties, Inc. and Claytone SF, a productof Southern Clay Products. Further, such organophilic clays may be ionexchanged clays; see, for instance, U.S. Patent Publication No.20010056149, herein incorporated by reference.

Said formulation (A) may have a viscosity, measured as describedhereinafter, of less than 1000 cP. The viscosity may be at least 200 cP.

Viscosity is suitably measured at 511 sec⁻¹ with a Fann Model 35 typeviscometer with an F1 spring, B1 bob, and R1 rotor at (25° C. and apressure of 1 atmosphere).

The sum of the wt % of said fluid (D), for example said inverse emulsionand the wt % of said particles in formulation (A) may be at least 80 wt%, at least 90 wt % or at least 95 wt %. The balance may include forexample a said suspending agent and/or other additives conventionallyused in fracturing fluids, for example biocides.

In a preferred embodiment, said formulation (A) includes:

70 to 90 wt % of said fluid (D), for example said inverse emulsion;

10 to 30 wt % of said particles; and

0 to 1 wt % of suspending agent.

The formulation (A) may include less than 1 wt % of a surfactant; andmay include at least 0.01 wt % of a surfactant.

The formulation (A) is preferably contacted with water to produce afracturing fluid. Thus, the invention extends, in a second aspect, to amethod of making a fracturing fluid, the method comprising contactingformulation (A) with water. As a result of the contact and/or mixing offormulation (A) with water, the inverse emulsion inverts and polymer (A)mixes with and/or is solubilised by the water. The fracturing fluid soformed exhibits a lower friction in use compared to that of water alone(and compared to use of, for example, an inverse emulsion comprisingpolymer (B), in the absence of particles of polymer (C)) and/or suchlower friction may be achieved rapidly on contact between formulation(A) and water.

Advantageously, it is found that said formulation (A) can readily bedispersed in the fracturing fluid without forming lumps of particles ofpolymer (C).

Water which is mixed with formulation (A) and/or which forms the majorpart of a fracturing fluid described herein may be derived from anyconvenient source. It may be potable water, surface water, sea water,brine, flow-back water, aquifer water or produced water. Referencesherein to amounts of water, particularly in the context of water whichforms a major part of a fracturing fluid described, suitably refer towater inclusive of components present in the source of water, such asdissolved salts found in sea water.

The method may comprise making a fracturing fluid which includes 25 to5,000 ppm, 25 to 1000 ppm or 250 to 1000 ppm of formulation (A) in anaqueous liquid, for example water.

In the method, other additives may be contacted with formulation (A)after and/or concurrently with water. Said other additives may beselected from corrosion inhibitors, proppant particulates, acids, fluidloss control additives, biocides, surfactants and scale inhibitors, claycontrol additives, foamers, paraffin inhibitors, gelling agents, pHadjustment additives, buffers, cross-linkers, oxidizing agents, enzymesand gel degrading agents.

Preferably, at some stage in the method, one or a plurality of proppantsis incorporated into the fracturing fluid. The proppant may have a sizeof at least 140 US Mesh; it may have a size of less than 5 US Mesh. Theproppant may be selected from sand, bauxite, and man-made intermediateor high strength materials. The proppant is arranged to restrict closedown of a fracture on removal of hydraulic pressure which caused thefracture.

Preferably, at some stage in the method, said fracturing fluid includes2.9 to 54 wt %, for example 5 to 40 wt %, of proppants.

According to a third aspect of the invention, there is provided afracturing fluid (e.g. a slick water fracturing fluid), said fracturingfluid comprising:

water soluble polymer (B);

water soluble polymer (C);

a hydrophobic liquid, suitably derived from said fluid (D) (e.g. saidinverse emulsion) as described in the first aspect; and

water.

Said fracturing fluid may be made as described in the second aspect.Said water soluble polymer (B), said water-soluble polymer (C) and saidhydrophobic liquid may be as described in the first aspect. Saidfracturing fluid may include any component included in formulation (A)of the first aspect from which it may be derived.

Said fracturing fluid (disregarding any and all proppant that may beincluded in the fluid) may include at least 99 wt % water.

According to a fourth aspect of the invention, there is provided amethod of fracturing a subterranean formation, the method comprisingcontacting the formation with a fracturing fluid made in a method of thesecond aspect and/or as described in the third aspect.

Said method preferably comprises fracturing a subterranean formationpenetrated by a well by pumping into the well at a pressure sufficientto create a fracture network the fracturing fluid.

According to a fifth aspect of the invention, there is provided a methodof manufacturing a formulation (A) according to the first aspect, themethod comprising:

(a) selecting a fluid (D) comprising an oil phase (e.g. an inverseemulsion comprising an oil-phase and a water-soluble polymer (B)); and

(b) contacting said fluid (D) (e.g. said inverse emulsion) withparticles of a water-soluble polymer (C).

Except for any water associated with said fluid (D) (e.g. said inverseemulsion), said method is preferably carried out in the presence of lessthan 5 wt % water. Suitably, no water is mixed with said fluid (D) (e.g.said inverse emulsion) and polymer (C) in the method.

Advantageously, it is found that said particles of polymer (C) canreadily be dispersed in fluid (D) without forming lumps of particles ofpolymer (C).

According to a sixth aspect of the invention, there is provided anassembly positioned adjacent a subterranean formation and arranged todeliver a fracturing fluid into the formation, said assembly comprising:

(I) a receptacle containing formulation (A) according to the firstaspect;

(II) a water supply;

(III) a pump (PI) for dosing formulation (A) from said receptacle intosaid water supply, suitably to define at least part of a fracturingfluid;

(IV) a conduit for delivering fracturing fluid into the formation; and

-   -   (V) a pump (P2) for injecting the fracturing fluid via said        conduit into the formation.

Any aspect of any invention described herein may be combined with anyfeature described in any other aspect of any invention or embodimentdescribed herein mutatis mutandis.

BRIEF DESCRIPTION OF THE FIGURES

Specific embodiments of the invention will now be described, by way ofexample, with reference to the accompanying figures, in which:

FIG. 1 is a particle size distribution graph (percent volume v. particlediameter (μm)) for Granule Polyacrylamide (GP);

FIG. 2 is a graph of % Friction Reduction v. time for formulationsdescribed in Example 3;

FIG. 3 is a graph of % Friction Reduction v. time for formulationsdescribed in Example 4;

FIG. 4 is a graph of % Friction Reduction v. time for formulationsdescribed in Example 5; and

FIG. 5 is a graph of % Friction Reduction v. time for formulationsdescribed in Example 6.

WORKING EXAMPLES

The following materials are referred to hereinafter:

Emulsion polymer (EP)—commercially available emulsion friction reducercomposition supplied as FliRate 605 available from Independence OilfieldSpecialties and comprising approximately 20 wt % of an anionic partiallyhydrolysed polyacrylamide copolymer, present as an inverse emulsion withwater and surfactant in approximately 25 wt % of a continuous oil phasecomprising a hydro treated light petroleum distillate.

Organophilic Clay (OC)—Claytone SF from BYK

Granule polyacrylamide (GP)—commercially available particulate frictionreducer composition comprising >90% of an anionic partially hydrolysedpolyacrylamide copolymer. Particle size analysis of the material isprovided in FIG. 1. Analysis was performed using a Beckman Coulter LaserParticle Size Analyser LS13320. The material has a volume medianparticle diameter of 320.8 μm, a volume mean particle diameter of 323.2μm, the largest particles being 948 μm and the smallest being 27.4 μm

Test Water (W)—refers to tap water having the following composition.

Concentration Ions (mg/L) Calcium 13.80 Magnesium 1.64 Barium 0.05 Boron0 Iron 0 Sodium 244.56 Chloride 226.27 Sulphate 16.50 Phosphates 0.06Bicarbonate 280.60 Carbonate 6.40 Potassium 2.93 Silicon 9.42 pH 8.90Specific Gravity 1.00 Total Dissolved Solids (ppm) 811.64

In general terms, formulations for fracturing fluids are prepared bymixing a granulated water-soluble friction reducing polymer (Granulepolyacrylamide (GP)) with an invert polymer emulsion friction reducingformulation (Emulsion Polymer (EP)), optionally in the presence of anorganophilic clay, without the need for specialized field equipment. Themixture can be dosed into water to produce a fracturing fluid which isfound to be technically highly advantageous and cost-effective.

Example 1 describes the preparation of candidate formulations fortesting, Example 2 describes a general procedure for Flow-loop testing.Examples 3 to 6 describe assessments undertaken and results for a rangeof formulations.

Example 1—Preparation of Candidate Formulations for Testing

The following blends A-1, A-2, A-3 and B-1 were prepared by blending thecomponents described in the table at the level indicated to produceslurries having densities and viscosities as detailed in Table 1. Ingeneral terms in the method, the clay is added to Emulsion Polymer (EP)to disperse and activate the clay. The Granule Polyacrylamide (GP) isadded and mixture stored at ambient temperature and pressure.

TABLE 1 Granule Emulsion Organo- Poly- Polymer philic acrylamide SlurryFormulation Density (EP) Clay (OC) (GP) Viscosity Identifier. (lb/gal)(wt %) (wt %) ((wt %)) (cP) Blend A-1 8.942 79.30 0.51 20.19 378 BlendA-2 8.946 79.42 0.35 20.22 349 Blend A-3 8.937 79.61 0.20 20.18 340Blend B-1 8.875 81.55 0.35 18.11 320

Example 2—General Procedure for Flow-Loop Testing of Formulations

A flow loop device used was composed of two 10 ft pipes in sequence, one% inch and the other ½ inch. The water for the test was held in a 5gallon reservoir tank, equipped with an overhead stirrer. The fluid wasrecirculated through the pipes and reservoir using a Moyno pump. Theflow rate in each test was held constant at either 6 or 10 gal/min.Initially, Test Water (W) was pumped for two minutes at constant rate toestablish a baseline. After two minutes, a friction reducer to be testedwas added to the reservoir tank with 30 seconds of vigorous mixing toassure uniform distribution of friction reducer while also flowingthrough the flow loop plumbing. After the 30 seconds of vigorous mixing,the stirrer speed was reduced to gently mix components for the rest ofthe test.

The pressure drop across the length of each pipe, the flow rate througheach pipe and the fluid temperature was continuously recorded, with databeing collected at a rate of one data point per second. Each test wasrun for about 18 minutes. At the completion of each test, the flow rate,temperature and the percent friction reduction (calculated as 1−(ΔPFR/ΔP water), were plotted against time.

Example 3—Assessment of Formulations (First Set of Experiments)

In the first set of experiments, testing of formulations detailed in theTable 2 below was undertaken using the flow loop of Example 2, at a flowrate of 6 gal/min.

TABLE 2 Inversion Max % Example Formulation Loading Viscosity TimeFriction No. Identifier (gpt) (cP) pH (sec) Reduction 3a Emulsion 0.501.13 8.05 62 73 (Comparative) Polymer (EP) 3b Emulsion 0.25 0.98 8.09 7069 (Comparative) Polymer (EP) 3c Blend A-1 0.25 1.17 8.02 22 73 3d BlendA-2 0.25 1.17 8.00 21 73 3e Blend A-3 0.25 1.16 8.03 22 73 Note that“gpt” refers to “gallons per thousand gallons” which is conventional inthe art.

Results of the flow loop test are provided in Table 1 and in FIG. 2. Theresults show that the maximum friction reduction for the base line 0.50gpt (Example 3a) was 73%, and the inversion time was 62 sec. When halfthe amount, 0.25 gpt in Example 3b was compared, the maximum reductionwas only 69% and the inversion time was 70 sec. However, byincorporating varying amounts of powdered friction reducer polymer (i.e.Granule Polyacrylamide (GP)) in the Emulsion Polymer (EP) as describedin Examples 3c, 3d and 3e, the maximum friction reduction is 73% and theinversion time is significantly faster (21-22 sec) compared to theExample 3b formulation which does not include the Granule Polyacrylamide(GP), but only includes Emulsion Polymer (EP).

FIG. 2 illustrates the slower inversion rates of the Example 3a and 3bformulations compared to the formulations of Examples 3c to 3e, whichinclude various amounts of Granule Polyacrylamide (GP). In addition, theExample 3c to 3e formulations, each of which contains about 20 wt %powdered polyacrylamide and varying amounts of organophilic clay, shownear identical performance with all three curves in FIG. 2 lying on topof one another.

Example 4—Assessment of Formulations (Second Set of Experiments)

In a second set of experiments, testing of formulations detailed inTable 3 was undertaken following the procedure of Example 3, but using,as a base line, 0.25 gpt of a formulation which only includes EmulsionPolymer (EP). This is Example 4a (comparative). This is compared toExample 4b (comparative) which uses a reduced concentration of 0.1 gptof Emulsion Polymer (EP) formulation and to a concentration of 0.1 gptof Blends A-1, A-2 and A-3 as described in Examples 4c, 4d and 4e. Table3 below summarises details of the formulations used in the experimentsand results obtained which are represented graphically in FIG. 2.

TABLE 3 Inversion Max % Example Formulation Loading Viscosity TimeFriction No. Identifier (gpt) (cP) pH (sec) Reduction 4a Emulsion 0.250.98 8.09 70 69 (Comparative) Polymer (EP) 4b Emulsion 0.1 0.84 8.12 10853 (Comparative) Polymer (EP) 4c Blend A-1 0.1 0.99 7.98 27 72 4d BlendA-2 0.1 0.99 8.16 29 72 4e Blend A-3 0.1 0.97 8.02 28 73

The results detailed in Table 2 and FIG. 3 show, for Example 4a (whichincludes only the Emulsion Polymer (EP) at 0.25 gpt), a 60% maximumfriction reduction and a 70 sec inversion time. When dropping theloading to 0.1 gpt of Emulsion Polymer (EP) (Example 4b), theperformance suffered, with the maximum friction reduction declining to53% and the inversion time increasing to 108 sec—both of these factorswould cause high pumping pressure on a fracturing treatment. Incontrast, Examples 4c, 4d and 4e show that Blends A-1, A-2 and A-3provide 72% maximum friction reduction with an inversion time of 27-29sec which results are superior to those for Examples 4a and 4b and evensuperior to Example 3a (Comparative) which uses Emulsion Polymer (EP) atthe much higher loading of 0.5 gpt.

Example 5—Assessment of Formulations (Third Set of Experiments)

The procedure of Example 3 was repeated using a higher flow rate of 10gal/min. The results are detailed in Table 4 below and FIG. 3 andcompare use of base emulsions (Emulsion Polymer (EP)) (Examples 5a and5b) with formulations comprising blends of Emulsion Polymer (EP) andGranule Polymer (GP).

Results show use of Emulsion Polymer (EP) alone at 0.5 gpt (Example 5a)produces 72% maximum friction reduction and 106 sec inversion. Reducingthe loading of Emulsion Polymer (EP) to 0.25 gpt (Example 5b) produces59% maximum reduction and an inversion time of 141 sec. In contrast,formulations which include Emulsion Polymer (EP) and GranulePolyacrylamide (GP) at 0.25 gpt shows 73-76% maximum reduction and aninversion time of 19-28 sec, this being both more effective and moreaffordable than higher loadings of the base emulsion.

Example 6—Assessment of Formulations (Fourth Set of Experiments)

In the next experiment, the performance of Blend A-2 is compared toBlend B-1. The test was conducted at a flow rate of 10 gal/min using0.25 gpt and 0.1 gpt of the emulsions. The data is shown in Table 4. Asper the table, there are slight differences between blends B-1 and A-2at 0.25 gpt. However, Blend A-2 gave slightly better performance thanblend B-1 at 0.10 gpt loading.

TABLE 4 Inversion Max % Example Formulation Loading Viscosity TimeFriction No's Identifier (gpt) (cP) pH (sec) Reduction 6a Blend B-1 0.101.0 8.36 25 72 6b Blend A-2 0.10 0.96 8.17 26 74 6c Blend B-1 0.25 1.168.22 20 76 6d Blend A-2 0.25 1.18 8.10 19 76

Results are also summarised in FIG. 5.

As an alternative to the Granule Polyacrylamide (GP) being mixed withEmulsion Polymer (EP), the Granule Polyacrylamide (GP) may be added toother non-aqueous additives which are used in fracturing process. Thesemay include non-aqueous guar slurries and non-aqueous cross-linkingagents.

Example 7—Use in Horizontal Well

The product blend defined in Example 1 as Blend A-1 was used on severalhorizontal wells as a way to achieve a significant decrease in treatingpressure during the hydraulic fracturing completion process. Aparticular well was 12,300 ft and constructed with 5.5 inch diametercasing. The fracture design for these wells led with 8,400 galslickwater pad followed by roughly 483,000 gal of slickwater fluid at arate of 3,780 to 4,200 gal treating fluid per min using Blend A-1 todisplace 600,000+ lbs of frac sand. The Blend A-1 product was pumped atrates ranging from 0.7 to 1.0 gal/1000 gal treating fluid, depending ontreating pressure. In addition to the friction reducer, the treatingfluid also comprised 0.15 gal/1000 gal organophosphonate scale inhibitorand 0.25 gal/1000 gal 50% aqueous glutaraldehyde solution as a biocide.The frac sand proppant concentration was ramped upward through the jobfrom 0.5 to 2.25 lb/gal added.

Blend A-1 was provided in 330 gal plastic “one-way” totes plumbed fromthe bottom of the tote via a 2″ cam lock connection. The totes werelocated on top of a flat-bed trailer or a tote rack which utilized thehydrostatic pressure to aid in product flow to the chemical pump. The 2inch diameter chemical hoses were then run from the tote to a mediumrange Waukesha pump. A diaphragm pump was used at times to prime thechemical line, depending on distances from the chemical injection pumps.Once the line was primed, the diaphragm pump was removed. The preferableinjection point for Blend A-1 was the suction side of the blenderdischarge pump. However, the pumping company blender did not have anavailable port, so Blend A-1 was pumped from the Waukesha pump into thetub portion of the pumping company's blender. The Waukesha pumpsdischarge the product through the 2 inch diameter chemical lines roughly20 ft to the blender tub.

Blend A-1 was pumped as the only friction reducer and achieved theoperator's goal of significant reduction of treating pressure. Thetreating pressures range from 7,500-9,500 psi, averaging 8,800-9,200 psiat 3,780 to 4,200 gal of treating fluid per min. This pressure at theseinjection rates was a significant improvement over conventionalemulsion-based friction reducers, typically these having the samepressures at lower rates, such as 2,940 to 3,360 gal per min.

It will be appreciated from the above examples that use of formulationscomprising Emulsion Polymer (EP) and Granule Polyacrylamide (GP), aresignificantly advantageous over use of Emulsion Polymer (EP) alone. Forexample, the time taken between initial introduction of the formulationsinto water and maximum friction reduction is lower than when EmulsionPolymer (EP) alone is used and the maximum % friction reduction achievedfor the formulations is higher than for an equivalent loading ofEmulsion Polymer (EP) alone. The aforementioned allows pumps used toinject fracturing fluids incorporating the formulations to be operatedat reduced speeds and/or pressures; or greater friction reduction may beachieved for a given pump speed/pressure, thereby allowing fracturefluids to be delivered at a higher pressure at the fracture face.

Additionally, since the formulations described use less of relativelycostly Emulsion Polymer (EP), friction reducer costs can besignificantly reduced without the need for specialist field equipmentand associated fuel and personnel costs.

The invention is not restricted to the details of the foregoingembodiment(s). The invention extends to any novel one, or any novelcombination, of the features disclosed in this specification (includingany accompanying claims, abstract and drawings), or to any novel one, orany novel combination, of the steps of any method or process sodisclosed.

1. A formulation (A), for use in a fracturing fluid, comprising: (i) afluid (D) comprising an oil phase; and (ii) particles of a water-solublepolymer (C).
 2. The formulation (A) according to claim 1, wherein saidfluid (D) is an inverse emulsion comprising a water-soluble polymer (B)and said oil phase.
 3. The formulation (A) according to claim 2, whereinsaid polymer (B) includes acrylamide repeat units.
 4. The formulation(A) according to claim 3, wherein said polymer (B) includes a repeatunit which includes an optionally substituted acrylamide of formula I

wherein R⁵, R⁶ and R⁷ independently represent a hydrogen atom or anoptionally-substituted C₁₋₄ alkyl group in combination with: a repeatunit comprising a moiety of formula II

wherein the O* moiety is an O⁻ moiety or is covalently bonded to anotheratom or group; a repeat unit comprising a vinyl pyrrolidone moiety; or arepeat unit comprising a moiety of formula III

wherein R¹ and R² are independently selected from a hydrogen atom and anoptionally-substituted alkyl group.
 5. The formulation (A) according toclaim 2, wherein the inverse emulsion comprises at least 15 wt % of saidoil phase; and less than 70 wt % of said oil phase.
 6. The formulation(A) according to claim 2, wherein said inverse emulsion comprises atleast 15 wt % and less than 50 wt % of polymer (B).
 7. The formulation(A) according to claim 6, wherein polymer (B) incorporates up to 40 wt %of water.
 8. The formulation (A) according to claim 2, wherein saidinverse emulsion includes 15-40 wt % of said oil phase, 15-40 wt % ofpolymer (B) and 15-40 wt % water.
 9. The formulation (A) according toclaim 3, wherein said polymer (B) is an ionic polyacrylamide.
 10. Theformulation (A) according to claim 9, wherein said polymer (B) includes5-40 mol % of ionic repeat units.
 11. The formulation (A) according toclaim 2, wherein said polymer (B) includes a repeat unit which includesan acrylate, sulfonate or pyrrolidone moiety.
 12. The formulation (A)according to claim 2, wherein said oil phase comprises a hydrophobicliquid.
 13. The formulation (A) according to claim 2, wherein said watersoluble polymer (C) includes one or more moieties selected from—C(O)NH₂, —COO⁻, and quaternary ammonium.
 14. The formulation (A)according to claim 2, wherein said water soluble polymer (C),independent of said polymer (B), includes a repeat unit which includesan optionally substituted acrylamide of formula I

wherein R⁵, R⁶ and R⁷ independently represent a hydrogen atom or anoptionally-substituted C₁₋₄ alkyl group in combination with: a repeatunit comprising a moiety of formula II

wherein the O* moiety is an O⁻ moiety or is covalently bonded to anotheratom or group; a repeat unit comprising a vinyl pyrrolidone moiety; or arepeat unit comprising a moiety of formula III

wherein R¹ and R² are independently selected from a hydrogen atom and anoptionally-substituted alkyl group.
 15. The formulation (A) according toclaim 1, wherein said polymer (C) is an ionic polyacrylamide.
 16. Theformulation (A) according to claim 15, wherein said particles of watersoluble polymer (C) have a mean particle diameter of at least 100 μm.17. The formulation (A) according to claim 1, wherein a ratio (X),defined as the pbw of said fluid (D) divided by the pbw of saidparticles is in the range 1-12.
 18. The formulation (A) according toclaim 2, wherein a ratio (Y), defined as the pbw of polymer (B) dividedby the pbw of polymer (C) is in the range 5:1 to 1:5.
 19. Theformulation (A) according to claim 18, wherein a ratio (Z), defined asthe pbw of said oil phase divided by the pbw of polymer (C) is in therange 0.1-2.0.
 20. The formulation (A) according to claim 9, furthercomprising a suspending agent to facilitate suspension of said particlesin the formulation.
 21. The formulation (A) according to claim 9,wherein said formulation (A) has a viscosity of less than 1000 cP. 22.The formulation (A) according to claim 20, wherein said formulation (A)includes: 70-90 wt % of said fluid (D); 10-30 wt % of said particles;and 0 to 1 wt % of suspending agent.
 23. A method of fracturing asubterranean formation, the method comprising contacting the formationwith a fracturing fluid which comprises formulation (A) of claim 1 incombination with an aqueous liquid.
 24. A method of manufacturing aformulation (A) according to claim 1, the method comprising: (a)selecting a fluid (D) comprising an oil-phase and a water-solublepolymer (B) wherein said fluid (D) is an inverse emulsion comprisingsaid water-soluble polymer (B) and said oil phase; and (b) contactingsaid a fluid (D) with particles of a water-soluble polymer (C).